JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY

Biodegradable Polylactide/Montmorillonite
Nanocomposites
Suprakas Sinha Ray,a, * Kazunobu Yamada,b Masami Okamoto,a, * and Kazue Uedab
a
Advanced Polymeric Materials Engineering, Graduate School of Engineering, Toyota Technological Institute, Nagoya 468 851, Japan
b
Unitika Ltd., Kyoto 611 0021, Japan

Our continuing research on the preparation, characterization, materials properties, and biodegrad-
ability of polylactide (PLA)/organically modified layered silicate (OMLS) nanocomposites has yielded
results on PLA /montmorillonite nanocomposites. Montmorillonite (mmt) modified with dimethyldioc-
tadecylammonium cation was used as an OMLS for nanocomposite preparation. The internal struc-
ture of nanocomposites on the nanometer scale was established with the use of wide-angle X-ray
diffraction patterns and transmission electron micrographic observation. All nanocomposites exhib-
ited significant improvement in crystallization behavior, mechanical properties, flexural properties,
heat distortion temperature, and O2 gas permeability when compared with pure PLA.

Keywords: Polylactide, Montmorillonite, Nanocomposite, Crystallization, Materials Properties.

1. INTRODUCTION in mequiv/100 g). This charge is not locally constant, as it

Over the last few years, polymer/layered silicate nanocom-
posites have attracted great interest from researchers, both in
industry and in academia, because they often exhibit remark-
able improvement of materials properties when compared
varies from layer to layer and must rather be considered as
an average value over the whole crystal. Layered silicates
have two types of structure, tetrahedral-substituted and octa-
hedral-substituted. In case of tetrahedral-substituted layered
silicates the negative charge is located on the surface of sili-

with pure polymer or conventional composites (both micro-
and macro-composites). These improvements include higher
moduli,1 increased strength and heat resistance,2 decreased
gas permeability3 and flammability,4 and increased biodegra-
dability of biodegradable polymers.5 On the other hand,
these materials have also been proved to be unique model
systems for the study of the structure and dynamics of poly-
mers in confined environments.6
The commonly used layered silicates for the preparation
of polymer/layered silicate nanocomposites belong to the
same general family of 2:1 layered or phyllosilicates.7 Their
crystal structure consists of layers made up of two silica
tetrahedra fused to an edge-shared octahedral sheet of either
aluminum or magnesium hydroxide. The layer thickness is
around 1 nm, and the lateral dimensions of these layers may
vary from 30 nm to several micrometers and even larger,
depending on the particular layered silicate. Stacking of the
layers leads to a regular van der Waals gap between the
layers called the interlayer or gallery. Isomorphic substitu-
tion within the layers (for example, Al3
replaced by Mg2

or by Fe2
, or Mg2
replaced by Li
) generates negative
charges that are counterbalanced by alkali and alkaline earth
cations situated inside the galleries. The type of layered sili-
cate is characterized by a moderate surface charge (known
as cation exchange capacity (CEC), and generally expressed
*Authors to whom correspondence should be addressed.
J. Nanosci. Nanotech. 2003, Vol. 3, No. 6 © 2003 by American Scientific Publishers
RESEARCH ARTICLE
cate layers, and, hence, the polymer matrices can react with
tetrahedral-substituted silicate more compared with that of
octahedral-substituted.7
Pristine layered silicates usually contain hydrated Na

or K
ions.8 Obviously, in this pristine state layered sili-
cates are only miscible with hydrophilic polymers, such as
poly(ethylene oxide) (PEO),9 poly(vinyl alcohol) (PVA),10
etc. To render layered silicates miscible with other polymer
matrices, one must convert the normally hydrophilic silicate
surface to organophilic, which makes possible the interca-
lation of many engineering polymers. Generally, this can be
done by ion-exchange reactions with cationic surfactants,
including primary, secondary, tertiary, and quaternary alkyl-
ammonium or alkylphosphonium cations. The role of alkyl-
ammonium or alkylphosphonium cations in the organosil-
icates is to lower the surface energy of the inorganic host
and to improve the wetting characteristics with the polymer
matrix; this results in a larger interlayer spacing. Addi-
tionally, the alkylammonium or alkylphosphonium cations
could provide functional groups that can react with the
polymer matrix or in some cases initiate the polymeriza-
tion of monomers to improve the strength of the interface
between the inorganic and the polymer matrix.11, 12
The main reason for the improved properties of pure poly-
mer in nanocomposites is interfacial interaction between
polymer matrix and organically modified layered silicate
(OMLS) as opposed to conventional composites. A few
1533-4880/2003/03/001/008/$17.00+.25 doi:10.1166/jnn.2003.220 1
 Ray et al./Biodegradable Polylactide/Montmorillonite
weight percent of OMLS that is properly dispersed through-
out the matrix thus creates a much higher surface area for
polymer-filler interfacial interactions than do conventional
composites.13 On the basis of the strength of polymer-
OMLS interactions, three different types of nanocomposites
are structurally achievable: intercalated nanocomposites,
where insertion of polymer chains into the layered silicate
structure occurs in a crystallographically regular fashion,
regardless of the polymer-to-OMLS ratio, and a repeat dis-
tance of few nanometers; flocculated nanocomposites,
where intercalated stacked silicate layers eventually floc-
culate because of the hydroxylated edge-edge interactions;
and exfoliated nanocomposites, where the individual sili-
cate layers are separated in a polymer matrix by average
distances that totally depend on the clay loading.14
Recently, the development of biodegradable polymeric
materials with excellent materials properties is a subject of
great research challenge in materials science. One of the
most promising polymers in this direction is polylactide
(PLA) because it is made from renewable agriculture
products and is readily biodegradable.15, 16 PLA is linear
aliphatic thermoplastic polyester, produced by the ring-
opening polymerization of lactide.17–19 Lactide is a cyclic
dimer prepared by the controlled depolymerization of lac-
tic acid, which in turn is obtained by the fermentation of
corn, sugar beet, etc.15, 16 It has very good mechanical
properties, thermal plasticity, fabric ability, and biocom-
patibility.20–21 Even when burned it produces no nitrogen
oxide gases and only one-third the combustible heat gener-
RESEARCH ARTICLE
ated by polyolefin, and does not damage incinerators and,
thus, provides significant energy savings.22 So PLA is a
promising polymer for various end-use applications, and
currently there is increasing interest in using PLA for dis-
posable degradable plastic articles.23 However, some other
properties such as heat distortion temperature (HDT), flex-
ural and gas barrier properties, and melt viscosity for fur-
ther processing are frequently not good enough for wide-
ranging applications.24 On the other hand, preparation of
naocomposites with OMLS has already proved to be an
effective way to improve these properties significantly.1–6
In our previous papers,25–29 we have reported on the
preparation, characterization, and materials properties of
various kinds of PLA/OMLS nanocomposites. In this
paper we describe the preparation, characterization, crys-
tallization behavior, mechanical and material properties of
another type of PLA nanocomposite prepared with dimeth-
yldioctadecylammonium-modified montmorillonite with a
simple melt extrusion technique.
2. EXPERIMENTAL DETAILS
2.1. Materials
PLA with D content of 1.1–1.7% (supplied by Unitika Co.
Ltd., Japan) was dried under vacuum at 60 °C and kept
under dry nitrogen gas for 1 week prior to use. The organ-
2
J. Nanosci. Nanotech. 2003, 3, 1–5
ically modified montmorillonite (C2C218-mmt) used in this
study was supplied by Hojun Yoka Co., Japan, and was
synthesized by replacing Na
in montmorillonite (mmt)
(original thickness of
1 nm and average length of 100 nm)
of a CEC of 90 mequiv/100 g with dimethyldioctadecy-
lammonium cation by ion exchange reaction.
2.2. Nanocomposite Preparation
For nanocomposite preparation, C2C218-mmt (powder form)
and PLA (pellet form) were first dry-mixed by shaking
them in a bag. The mixture was then melt-extruded with a
twin-screw extruder (PCM-30, Ikegai machinery Co.) oper-
ated at 210 °C30 (screw speed  100 rpm, feed rate  120
g/min) to yield nanocomposite strands. Henceforth, the
product nanocomposites are abbreviated as PLACNs.
PLACNs prepared with three different amounts of C2C218-
mmt of 4, 5, and 7 wt% are correspondingly abbreviated
as PLACN4, PLACN5, and PLACN7, respectively. The
strands were pelletized and dried under vacuum at 60 °C for
48 h to remove water.
The dried PLACN pellets were then converted into sheets
with a thickness of 0.7–2 mm by pressing with
1.5 MPa at
190 °C for 3 min. The molded sheets were then quickly
quenched between glass plates and then annealed at 110 °C
for 1.5 h to crystallize isothermally before being subjected to
wide-angle X-ray diffraction (WAXD), transmission elec-
tron microscopy (TEM), and dynamic mechanical property
measurements.
2.3. Characterization
2.3.1. WAXD
WAXD analyses were performed for the C2C218-mmt
powder and three different PLACN sheets with an MXlabo
X-ray diffractometer (MAC Science Co., generator of 3 kW,
a graphite monochromator, CuKa radiation (wavelength,
l  0.154 nm), operated at 40 kV/20 mA). The samples
were scanned in fixed-time (FT) mode with a counting
time of 2 s under a diffraction angle of 2v in the range of
1° to 70°.
2.3.2. TEM
To clarify the nanoscale structure of various PLACNs,
high-resolution TEM (H-7100; Hitachi Co.) was also used,
at an accelerating voltage of 100 kV. An ultrathin section
of crystallized sheet (perpendicular to the compression
mold) with a thickness of
100 nm was microtomed at
80 °C with a Reichert Ultra cut cryo-ultramicrotome
without staining.
2.3.3. Gel Permeation Chromatography
Weight-averaged (Mw) and number-averaged (Mn) molec-
ular weights of PLA (before and after nanocomposite
J. Nanosci. Nanotech. 2003, 3, 1–5 Ray et al./Biodegradable Polylactide/Montmorillonite

preparation) were determined by gel permeation chroma-
tography (GPC) (LC-VP, Shimadzu Co.), with polystyrene
standards for calibration and tetrahydrofuran (THF) as the
carrier solvent at 40 °C, with a flow rate of 0.5 ml/min. For
the GPC measurements first PLA or nanocomposites were
dissolved in CHCl3 and then diluted with THF. In the case
of nanocomposites, after dissolving in CHCl3 the insoluble
clay particles were separated from the dissolved PLA by
filtration.
2.3.4. Differential Scanning Calorimetry
The glass transition (Tg), melting (Tm), and crystallization
(Tc) temperatures, as well as degree of crystallinity (xc)
of pure PLA and PLACNs, were determined by tempera-
ture-modulated differential scanning calorimetry (DSC)
(TMDSC) (MDSC, TA2920, TA instruments), operated at
a heating rate of 5 °C/min with a heating/cooling cycle of
the modulation period of 60 s and an amplitude of 0.769
°C. For the measurement of xc prior to DSC analysis, the
extra heat absorbed by the crystallites formed during heat-
ing had to be subtracted from the total endothermic heat
flow due to the melting of the whole crystallites. This can
be done according to the principles and procedures
described in our previous paper.31 By considering the
melting enthalpy of 100% crystalline poly(L-lactide) as
93 J/g,32 we have estimated the value of the xc for pure
PLA and PLACNs, which is presented in Table I.
and placed on a laboratory hot plate at 200 °C for 60 s
to obtain a thin film
30 mm in thickness. The molten film
was then quickly quenched to the desired temperature (100
°C) by putting it on a thermostatted hot stage (Linkam
RTVMS; Linkam Scientific Instruments, Ltd.) mounted on
a POM (Nikon OPTIPHOTO2-POL). After complete crys-
tallization, the nature of crystallite growth was observed
with a POM.
2.3.6. Dynamic Mechanical Analysis
Dynamic mechanical properties of the pure PLA and
PLACNs were measured with a Reometrics Dynamic Ana-
lyzer (RDAII) in the tension-torsion mode. The tempera-
ture dependence of dynamic storage modulus (G), loss
modulus (G), and their ratio, tan d, of pure PLA and vari-
ous PLACNs were determined at a constant frequency (q)
of 6.28 rad/s with a strain amplitude of 0.05%, and in the
temperature range of 20 to 160 °C with a heating rate of
2 °C/min.
2.3.7. Flexural Properties and Heat Distortion
Temperature
The sample pellets were injection-molded with an injec-
tion machine (IS-80G; Toshiba Machinery Co.) operated
at 190 °C with a mold temperature of 30 °C. Flexural mod-
ulus and strength of the injection-molded specimens (thick-
ness
3.2 mm, annealed at 120 °C for 30 min) were mea-

RESEARCH ARTICLE
2.3.5. Light Scattering and Polar Optical Micrographic sured according to the ASTM D-790 method (model 2020;
Observations Intesco Co.) with a strain rate of 2 mm/min at room tem-
perature (
25 °C). The heat distortion temperature (HDT)
To investigate the crystallite texture, the pure PLA and tests of neat PLA and various PLACNs were conducted
PLACN samples were subjected to light scattering (LS) with crystallized injection molded samples (HDT Tester;
experiments under Hv scattering mode with the radiation Toyoseiki Co.) according to the ASTM D-648 method
of a polarized He-Ne laser at 632.8-nm wavelength. The with a heating rate of 2 °C/min. We also conducted load
details of the LS measurement were described in our previ- dependence of HDT of neat PLA and PLACN7 by the
ous paper.33 same procedure.
We also observed the crystallite growth behavior of pure
PLA and PLACNs with a polar optical micrograph (POM).
2.3.8. Measurement of O2 Gas Transmission Rates
Dried pellets were sandwiched between two glass slides
Oxygen gas transmission rates of pure PLA and various
PLACNs were measured at 20 °C and 90% relative humid-
Table I. Characteristic parameters of neat PLA and various PLACNs.
ity by the ASTM D-1434 differential pressure method
Parameters Neat PLA PLACN4 PLACN5 PLACN7 (GTR-30XAU; Yanaco Co.). Test samples were prepared
3
Mw  10 (gmol ) 1
177 a
163 158 155
by compression molding (thickness
300 mm), and melt-
Mw/Mn 1.58 1.61 1.60 1.59 quenched samples were used for this measurement.
Tg (°C) 60 58.6 57.4 57.3
Tm (°C) 168 170 169.6 169.6
Tc (°C) 127.2 101 101.7 100.6 3. RESULTS AND DISCUSSION
xc (%) 36 47.5 47.2 51.7
N  105 (mm3) 2.7 822.6 337.4 207.9 3.1. Nanocomposite Structure
d001 (nm) — 3 2.95 2.85
D (nm)b — 11.3 14.5 15.9 The structure of the nanocomposites in the nanometer
D/d001 — 4 5 6 range has typically been elucidated by WAXD and TEM.
a
Extruded PLA under the same condition. WAXD provides direct evidence of the intercalation of
b
Calculated by using Scherrer equation. the polymer chains into the silicate galleries. On the other
3
 Ray et al./Biodegradable Polylactide/Montmorillonite
hand, TEM offers a qualitative understanding of the inter-
nal structure through direct visualization. WAXD patterns
for the pure C2C218-mmt powder and three different
PLACNs are presented in Figure 1. The interlayer gallery
height, calculated as the difference of the d001 distances
obtained by WAXD and the individual layer thickness for
the C2C218-mmt, is 2.5 nm, which, upon intercalation by
PLA, expands to
3 nm in the case of PLACN4. With
increasing clay content this distance gradually decreases,
and the value of d001 is equal to 2.85 nm in the case of
PLACN7. From the WAXD patterns, the crystallite size
(D) of intercalated stacked silicate layers of each PLACN
is calculated with the Scherrer equation.34 The calculated
value of D for each PLACN is also presented in Table I. It
is clearly established that the crystallite size (the thickness
of the dispersed stacked silicate layers) in the PLACNs
RESEARCH ARTICLE
Fig. 1. WAXD patterns of C2C218-mmt powder and various PLACNs.
The dashed line indicates the location of the silicate (001) reflection of
C2C218-mmt. The asterisks indicate the (001) peak for C2C218-mmt dis-
persed in PLA matrix.
4
J. Nanosci. Nanotech. 2003, 3, 1–5
gradually increases with increasing clay loading. There-
fore, we can conclude that the well-ordered intercalated
PLACNs were formed and coherence order of the silicate
layers increases with increasing C2C218-mmt content. Divid-
ing the value of D by the d001 value of each PLACN, we
can estimate the number of the stacked individual silicate
layers to be about 4 for PLACN4, 5 for PLACN5, and
about 6 in the case of PLACN7.
On the other hand, TEM is a qualitative tool used for the
determination of overall clay dispersion. Figure 2 shows
the typical bright-field TEM image of PLACN5 in which
dark entities are the cross section of the stacked and inter-
calated silicate layers.35 From the TEM image, we observed
the large anisotropy of the stacked and flocculated silicate
layers, which have an original thickness of
1 nm and an
average length of
100 nm.
3.2. GPC
GPC results of PLA in the pure state or in C2C218-mmt-
filled systems are also presented in Table I. As anticipated,
the incorporation of C2C218-mmt resulted in a reduction in
the molecular weight of the PLA matrix. Decreased mole-
cular weights of PLA in nanocomposites may be explained
by the shear mixing of PLA and C2C218-mmt, resulting
in a certain extent of hydrolysis of PLA matrix at high
temperature.
3.3. Thermal Properties and Crystallite Morphology
Figure 3 shows DSC traces for the melt-quenched samples
of neat PLA and three different PLACNs. These data are
obtained from the first run and during the heating process.
Samples were prepared by using a hot press. Neat PLA
and PLACN pellets were melted at 190 °C hold for 3 min
Fig. 2. High-resolution TEM bright-field image of crystallized PLACN5
sheet. The dark entities are the cross section of the intercalated mmt layers,
and the bright areas are the matrix.
J. Nanosci. Nanotech. 2003, 3, 1–5 Ray et al./Biodegradable Polylactide/Montmorillonite

Fig. 3. DSC scans of the melt-quenched samples of pure PLA and vari-
ous PLACNs.

at the same temperature under
1.5 MPa pressure, and

then quickly quenched between glass plates. From Figure
3 we can see an endothermic peak for all samples in the
temperature range of 55–60 °C. The temperature corre-
sponding to the endothermic peak for each sample is con-
sidered to be Tg of PLA. For all samples at Tg there is a
steplike change, which is due to enthalpy relaxation. This
type of steplike change at Tg has also been recognized for
some other polymers.36

On the other hand, all samples show an exothermic
peak, and that can be correlated to the crystallization of
PLA in every sample; the corresponding temperature is
known as the crystallization temperature, Tc. In the case of
PLACNs this peak is sharper and appeared at lower tem-
perature than that of neat PLA (see Table I). Therefore,
C2C218-mmt seems to enhance the rate of crystallization of
PLA. It should be noted here that Tc does not depend upon
C218C2-mmt. This behavior suggests that a small amount
of C2C218-mmt is enough to serve as a nucleating agent for
crystallization. A systematic DSC study of all samples
shows that the Tg signal of neat PLA gradually weakens
with increasing C2C218-mmt content. This behavior sug-
gests that C2C218-mmt layers affect all polymers, and there
is very small amount of bulk-like PLA present to manifest
itself through the thermal transition.
POM photographs of neat PLA and various PLACNs
are presented in Figure 4a. All samples were crystallized at
100 °C beforehand. Neat PLA exhibits well-defined large
crystallite morphology, whereas the size of the PLACN
crystallites is significantly smaller. This observation indi-
cates that the surface of dispersed C2C218-mmt has a very
strong effect on PLA crystallization.
This behavior is more clearly seen in LS patterns (see
Fig. 4b), where, for PLACNs, a clear large smeared four-
leaf-clover pattern is observed compared with the crystal-
lized neat PLA, indicating formation of a large number of
RESEARCH ARTICLE
Fig. 4. (a) Polarized optical micrographs of pure PLA and various
PLACNs isothermally crystallized at 100 °C for 1.5 h. (b) Hv-light scat-
tering patterns for pure PLA and various PLACNs isothermally crystal-
lized at 110 °C for 1.5 h.
less organized crystallites. From LS patterns, the number
of heterogeneous nuclei N can be estimated from a rough
approximation (i.e., all of the crystallites are of identical
size). The primary average nucleation density of the crys-
tallites, N, is given by37
N  (3/4p)(Dm/2)3
where Dm is the average maximum diameter of the crystal-
lite, that is, the attainable diameter before impingement.
The calculated values of N at 100 °C are also presented in
Table I. This behavior indicates that the surface of the dis-
persed C2C218-mmt layers acts as a nucleating agent for
PLA crystallization, which is evident from the increase in
the number of density of nuclei causing smaller crystallite
formation.37 So our investigation explores the role of
C2C218-mmt as a nucleating agent for PLA crystallization.
Such a discussion is beyond the objective of this paper, and
we will report it separately.38
5
 Ray et al./Biodegradable Polylactide/Montmorillonite
3.4. DMA
DMA measures the response of a given material to an oscil-
latory deformation (here in tension-torsion mode) as a func-
tion of the temperature. DMA results are expressed by three
main parameters: (a) the storage modulus (G), correspond-
ing to the elastic response to the deformation; (b) the loss
modulus (G), corresponding to the plastic response to the
deformation, and (c) tan d, that is, the G/G ratio, which is
useful for determining the occurrence of molecular mobil-
ity transitions such as the glass transition temperature.
Here DMA analysis has been studied to track the tem-
perature dependence of storage modulus upon PLACN
formation. Figure 5 shows the temperature dependence of
G, G, and tan d for PLA and corresponding PLACNs. For
all PLACNs, significant enhancement of G can be seen in
the investigated temperature range, indicating that interca-
lated PLACN is strongly influenced by the elastic proper-
ties of the PLA matrix.
Below Tg, the enhancement of G is clear in the inter-
calated PLACNs, but at the temperature range of 80 °C
to 145 °C all three nanocomposites exhibit much higher
enhancement of G as compared with that of pure PLA.
This is due to the mechanistic reinforcement by clay parti-
cles at high temperature. Above Tg, when materials become
soft, the reinforcement effect of the clay particles becomes
RESEARCH ARTICLE
Fig. 5. Temperature dependence of storage modulus (G), loss modulus
(G), and their ratio, tan d, for pure PLA and various PLACNs.
6
J. Nanosci. Nanotech. 2003, 3, 1–5
prominent and hence a strong enhancement of the modulus
appears.14, 39
On the other hand, above Tg the enhancement of G is
significant in the intercalated PLACNs in comparison with
that below Tg, indicating a plastic response to the deforma-
tion is prominent in the presence of clay when material
becomes soft. However, the presence of clay particles does
not lead to a significant shift and broadening of the tan d
curves for all PLACNs compared with that of pure PLA.
This behavior has been ascribed to the restricted segmental
motions at the organic–inorganic interface neighborhood
of intercalated PLACNs.
3.5. Flexural Properties and HDT
In Table II, we report the flexural modulus, flexural strength,
and distortion at break of neat PLA and three PLACNs mea-
sured at 25 °C. There is a significant increase of flexural
modulus for PLACN4 compared with that of pure PLA fol-
lowed by a constant value with increasing C2C218-mmt con-
tent. On the other hand, flexural strength and distortion at
break exhibited a remarkable increase with PLACN4 and
then gradually decreased with C2C218-mmt loading. This
behavior may be due to the high C2C218-mmt content, which
leads to a brittleness of materials. Therefore, we can control
the flexural strength and distortion by increasing or decreas-
ing OMLS content, and incorporation of C2C218-mmt of
around 4 wt% is the optimum for achieving a high value of
flexural strength and distortion.
The nanodispersion of C2C218-mmt in pure PLA also pro-
motes a higher HDT. We examined the HDT of pure PLA
and various PLACNs with different load conditions. As
seen in Figure 6a, in the case of PLACN4, there is a marked
increase in HDT with an intermediate load of 0.98 MPa,
from 76 °C for the pure PLA to 91.3 °C for PLACN4. The
value of HDT gradually increases with increasing clay
content, and, in the case of PLACN7, the value increases to
107 °C.
On the other hand, imposed load dependence on HDT is
clearly observed in the case of PLACNs. Figure 6b shows
the typical load dependence in the case of PLACN7. The
increase in HDT of neat PLA due to nanocomposite prepara-
tion is a very important property improvement, not only from
the industrial point of view but also for molecular control on
the silicate layers, that is, crystallization through interaction
between PLA molecules and SiO4 tetrahedral layers.
In the case of high load (1.81 MPa), it is very difficult to
achieve high HDT enhancement without strong interaction
Table II. Flexural properties of neat PLA and various PLACNs.
Flexural properties Neat PLA PLACN4 PLACN5 PLACN7
Modulus (GPa) 4.84 5.43 5.38 5.39
Strength (MPa) 86 102 107 99
Distortion (%) 1.9 3.9 2.1 1.9
J. Nanosci. Nanotech. 2003, 3, 1–5
Fig. 6. (a) Organoclay (C2C218-mmt) (wt%) dependence of HDT of pure
PLA and various PLACNs. (b) Load dependence of HDT of pure PLA and
PLACN7.
between polymer matrix and OMLS.40 In the case of all
PLACNs studied here, the values of Tm (cf. Table I) do not
change significantly as compared with that of pure PLA.
Furthermore, in WAXD analyses up to 2v  70° (see Fig. 7),
we observed no big shift or formation of new peaks in the
crystallized PLACNs. So the improvement of HDT with
intermediate load (0.98 MPa) originates from the better
mechanical stability of the PLACNs due to mechanical
reinforcement by the dispersed clay particles, higher value
of xc, and intercalation. This is qualitatively different from
the behavior of nylon-6/OMLS nanocomposites, where the
mmt layers stabilize in a crystalline phase different from
that found in the neat nylon-6, with a higher HDT.41
3.6. Oxygen Gas Permeability
Nanoclays are believed to increase the gas barrier proper-
ties by creating a maze or “tortuous path” that retards the
progress of gas molecules through the matrix resin.3, 42, 43
The mechanism for the improvement is attributed to the
increase in the tortuosity of the diffusive path for a pene-
trating molecule. Indeed, a simple tortuosity-based model
has been found to explain experimental trends satisfacto-
rily. The gas permeability of nanocomposites (PPLACN) is
related to the permeability of the pure PLA (PPLA) and the
volume fraction (fclay) and width (Dclay) of the dispersed
clay as44
PPLACN 1 as a function of organoclay (C2C218-mmt) content (wt%) measured at 20 °C

PPLA 1
( Lclay / 2 Dclay )f clay
Ray et al./Biodegradable Polylactide/Montmorillonite
Fig. 7. WAXD patterns of purePLA and various PLACNs. Samples were
crystallized at 110 °C for 1.5 h before measurements. The data were verti-
cally offset to make a clear presentation.
The above expression assumes that the sheets are placed
such that the sheet plane is perpendicular to the diffusive
pathway. The O2 gas permeability for the pure PLA and
various PLACNs are presented in Figure 8. As seen from
Figure 8, the permeability of O2 gas through the PLACN
films improved compared with pure PLA film.
4. CONCLUSIONS
RESEARCH ARTICLE
We have successfully prepared biodegradable polylactide/
C2C218-mmt nanocomposites by simple melt extrusion of
PLA and C2C218-mmt, wherein silicates of C2C218-mmt
are intercalated, stacked and flocculated, and nicely dis-
tributed in the PLA matrix. All nanocomposites exhibited
significant improvement in mechanical and various other
materials properties when compared with those of neat
PLA. These improvements include rate of crystallization,
mechanical and flexural properties, heat distortion tem-
perature, and O2 gas permeability. These concurrent prop-
erty improvements are well beyond what can be generally
Fig. 8. Oxygen gas permeability of pure PLA and various PLACN films
and 90% relative humidity.
7
 Ray et al./Biodegradable Polylactide/Montmorillonite
achieved through the micro/macro-composite preparation
or chemical modification of pure PLA.
Acknowledgment: Thanks are due to the Japan Society for
the Promotion of Science (JSPS) for the award of a postdoc-
toral fellowship and a research grant to S.S.R. (no. P02152).
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Received: 11 April 2003. Revised/Accepted: 1 May 2003.